Monazo intermediates



patented May 14, 1940 UNITED Z STATES PATENT OFFICE MONAZO IN TERMamATEs Miles Augustinus Dahlen and Frithjof Zwilgmeyer, Wilmington, du Pont de Nemours Del., 'assignors to E. I. & Company, Wilmington,

DeL, a corporation of Delaware No Drawing.

5 Claims.

This invention relates to monazo compounds,

and especially to certain phenyl-azo-amino naphthols 'which are insoluble in water and are" useful for preparing valuable insoluble monazo coupling components and other purposes.

It is an object of the invention to provide azo compounds which are especially useful "for the preparation of certain acylamino naphthol azo phenyl compounds, thelatter being valuable coupling components having aflinity for cotton fibres v and producing valuable dyeings when developed on the fibre with diazotized amino bases. Another object of the invention is to provide processes for preparing the novel compounds.

51 Other objects of the invention will be apparent from the following description.

The compounds of the invention are prepared a by diazotizing an aniline which is free from water solubilizinggroups and coupling in acid medium with a 1-amin'o-5-, -6-, or -'7-naphthol or with a 2-amino-6, -7- or -8-naphtho1. Commonly known methods of diazotization are used and the coupling isconducted in an acid medium which will cause; coupling on the ring of the naphthol which is substituted by amino.

The compounds of the invention are represented in general by the formula in which one Z is amino and the other is hydrogen, one Z1 is hydroxy and the others are hydroen, and R is the radicaloi abenzene compound which is mono substituted by amino and which is devoid of groups which make it soluble in water, but it may be substituted by other groups. I

The invention will be more fully set forth in the following more detailed description which includes examples that are given as illustrative embodiments of the invention andnot as limitations thereof Example 1 Meta-nitraniline (13.8 parts by weight) was diazotized in the usual manner. The solution of diazo salt was slowly added with stirring to a cold slightly acid solution of 175 parts of lamino-7-naphthol dissolved in hydrochloric acid. Before coupling the acid concentrations of the solutions were adjusted to give a reaction medium which was weakly acid to Congo red and then Application February 2, 1939, Serial No. 254,164

were cooled with ice to give a reaction medium which was about 0 C. to 5 C. The coupling was completein a short time and an azo compound which is represented by the following formula was precipitated and separated in the usual m 3.111! er When separated and dried, this compound was a reddish brown powder insoluble in water, soluble in aqueous caustic soda solutions and having affinity for cotton fibres upon which it can be "dyed and developed by applying diazotized amines. The compound can be acylated by heating a short time, say ten minutes at 120 C. with acetic anhydride. The acylated compound can then be used as a coupling component to make other developed dyeings having newshades and excellent improved properties.

Example 2 The same proportion of meta-nitraniline as in Example 1 was diazotized and coupled with 17.5 parts of l-amino-6-naphthol by a method similar to that of Example 1. The dried compound was a reddish brown powder having other properties and uses similar to the compound of Example 1. The compound is represented by the formula Similar results are obtained by coupling with 1,5-amino naphthol.

Example 3 was acylated and the acylated products were The compound is represented by the formula valuable coupling components and compared OCH 3 favorably with the products of the preceding ex- OaNON=N NH, amples- The compound is represented by the formula OCH:

H v Example 4 The same molecular proportion of 4-chloro-2- amino anisole as used in Example 1 was diazotized and coupled to 17.5 parts of 1,7-amino naphthol by .a process similar to that used-in Example 1.v The solubility of the product was similar to that of the compound of Example 1 and it had afi'inity' for cotton fibres upon which it could be satisfactorily developed with diazotized amines. jIt

By similar processes the following compounds were made. These compounds had in general-the aflinity, solubility, coupling and acylating properties of the compound of Example 1.

Arylamine diazotized Coupled to- Formula of product Aniline 1,7-amlno-naphthol ON=N NHI 4-chloro-2-az nino-anisnle an a-nitro-i-amlno-toluene 2,o-amlno-naphth0l....

Do 1,7-amlno-naphthol 4-chlom-z-amingfn'lnnnn (in 2,5-dichlo ro-nnilinn An 2-nitro-4-chloto-aniline. do WON: NH;

H CH;

4-nitro-2-am1'no-toluenn (In N= Arylamine diazotized l Coupled to- Formula ofproduct j Para-phenetidlne 1, 7-amino-naphthol.---. 0111 0 N= NHI 2,zi-dimemery-aniline.. -301.

Meta-nitto-anlllne 1,5-smlno-naphtho1 v N=N- NH M 3-nitro-4-amino-toluen fin z zo, 1 m, Do 2,6-amino-naphthol Meta-nitrodo 1;!0, NH: Do 2,7-amlno-naphthol--. ON=N Clv 2,5-dichloro-anlline 1,6-amino-naphthol The preferred embodiments of the invention are those in which the described coupling components are coupled to one of the diazotized anilines which is substituted once by alkyl, alkoxy, nitro or chloro in the metal or para posialkoxy or chloro and in the 4- or 5,-position by one of the group consisting of alkyl, alkoxy, nitro and chloro, such as para-nitraniline, 4-nitro-2- amino toluene, 5-nitro-2-amino toluene, 4-nitr0- 2-amino anisole, 5-nitro-2-amino anisole, 5- nitr0-2-amino anisole, 5-chloro-2-amino "toluene, 5-chloro-2-amino anisole, 3-nitro-6-chloro aniline, 4-nitro-2-chloro aniline, 3-chloro aniline, it-chloro aniline, 2-amino-4-chl'oro toluene, 2,5- dichlor aniline, 4-chloro aniline, 5-chloro-2- amino toluene, 5-chloro-2-amino anisole and 3,4- dichloro aniline. In the specification and claims .alkyl refers to aliphatic groups having not more hydroxy naphthalene.

As illustrations of other anilines which can be used the followingare mentioned, 2-nitro-6- methyl aniline, 2-nitro-6-methoxy aniline, 2,4-

We claim: 1. A compound represented by the formula R-N=N z in which one Z is amino and the other is hydrogen; one Z1 is hydroxy and the others are hydrogen; and R is the radical of one of a group consisting of the arylamines represented by the formulae Y i B i Y NH: and B Y i 1 3 NO:

wherein each Y is one of a group consisting of hydrogen, methyl, ethyl, methoxy, ethoxy, chloro and nitro; each X is one of a group consisting of hydrogen, methyl, ethyl, methoxy, ethoxy and chloro; at least one B is from the group consisting of methyl, ethyl, methoxy, ethoxy, chloro and nitro; and the other Bs are from the group consisting of hydrogen, methyl, ethyl, methoxy, ethoxy, chloro and nitro.

2. A compound represented by the formula in which R is the radical of one of a group consisting of the arylamines represented by the formulae Y X B B Y- NHz and B- NH:

I I Y X B N02 wherein each Y is one of a group consisting of hydrogen, methyl, ethyl, methoxy, ethoxy, chloro and nitro; each X is one of a group consisting of hydrogen, methyl, ethyl, methoxy, ethoxy and chloro; at least one B is from the group consisting of methyl, ethyl, methoxy, ethoxy, chloro and nitro; and. the other Bs are from the group consisting of hydrogen, methyl, ethyl, methoxy, ethoxy, chloro and nitro.

3. A compound represented by the formula 4. A compound represented by the formula OCH:

OzN- N 5. A compound represented by the formula OCHa MILES AUGUSTINUS DAHLEN. FRITHJ OF ZWILGMEYER. 

